In this work the determination of Cd, Cu, Cr, Fe and Sb as organic and inorganic additives in in-house plastic materials (ABS, LDPE) using electrothermal vaporization combined with inductively coupled plasma optical emission spectroscopy is described. The influence of CCl 2 F 2 as gaseous halogenation modifier was investigated. Especially for the carbide forming elements the sensitivity was improved and the memory effects were significantly reduced. Calibration was performed by external calibration and standard addition with aqueous standard solutions added directly into the sample boats. Absolute limits of detection (3s-criterion) range between 0.1 ng (Cd) and 9 ng (Fe) which corresponds to relative values of 0.1 mg kg À1 and 1.6 mg kg À1 , respectively, taking 5 mg as typical sample mass. The detection limits are sufficient to monitor the element contents of plastic materials according to European directives such as European directive on the safety of toys. The developed ETV-ICP-OES method allows a fast analysis with a high sample throughput (3 minutes per analysis), low sample consumption and good trueness and precision for the analyzed elements. Sample preparation is reduced to ashing the samples in a muffle furnace. Furthermore, measurements are possible regardless of the chemical form in the additives. For verification the results obtained with the developed method were compared with measurement results of independent methods ICP-MS/OES after digestion. In addition Cd, Cr and Pb were determined in a solid plastic reference material BAM-H010 to confirm the applicability and accuracy of the method.
The conventional quantitative method for the analysis of inorganic elements in polymer matrices is a complex and time consuming process that presents a significant risk for error. Typically, polymers are digested in a microwave oven or other devices under high temperature and pressure for several hours while employing different mixtures of high purity acids. In many cases, particularly when high concentrations of doped elements are present, the digestion is often incomplete and therefore the reproducibility depends strongly on the type of polymer and additives used. A promising alternative technology that allows for the direct analysis of these polymers without digestion is laser ablation ICP-MS. Due to a lack of available reference materials and the presence of matrix dependent effects, a precise calibration cannot be obtained. In order to compensate for the matrix dependent effects the use of internal standardization is necessary. In this study the correlation between the carbon released during the ablation process and the 13 C signal detected by ICP-MS and its use as an internal standard are investigated. For this purpose, twenty-one virgin polymer materials are ablated; the released carbon is determined and correlated with the corresponding integrated 13 C signal. The correlation resulted in a direct relationship between the ablated carbon and 13 C signal demonstrating the potential ability to neglect at least some of the matrix dependent and transport effects which occur during the laser ablation of virgin polymers.
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